CN107673338B - Method for preparing graphene by using waste graphite electrode - Google Patents
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Abstract
The invention discloses a method for preparing graphene by using waste graphite electrodes, which takes the waste graphite electrodes in the process of adding ionic bond metal salt to melt and electrolyze metal as raw materials, peels off graphite intercalated by metal on the surface layer of the waste graphite electrodes, intercalates part of the graphite at high temperature in the process of melting and electrolyzing the metal, and then carries out liquid phase delamination strengthening and fine stage centrifugal classification, and finally carries out separation, purification and drying to finally prepare the graphene. The graphene prepared by the method has few layers, large specific surface area and low energy consumption, changes waste into valuable, and has good economic value and social value.
Description
Technical Field
The invention belongs to the field of melting electrolysis graphite electrodes, and relates to a method for preparing graphene by using waste graphite electrode materials.
Background
The graphite electrode mainly comprises anthracite and a binder, and during the electrolysis process, the graphite electrode is modified, expanded and even damaged due to reactions caused during molten salt electrolysis such as high-temperature heating, metal ion intercalation, electrochemical intercalation, permeation of metal ions and electrolyte and the like. Taking the molten salt electrolytic aluminum process as an example, every ton of aluminum produced, 20kg to 30kg of waste graphite cathode will be produced.
At present, electrolytic aluminum factories in various countries around the world mostly adopt open-air stockpiling or landfill treatment on waste graphite cathode carbon blocks, and researchers also research and develop a series of treatment methods including a roasting method, a flotation method, a sulfuric acid decomposition method and the like, but the existing methods mainly focus on the harmless treatment of graphite cathodes, the treatment process is complex and the cost is high, the economic added value of the produced products is relatively low, and the economic value of the graphite electrodes cannot be fully utilized.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing graphene by using waste graphite electrodes, and the method has the advantages of low preparation cost, high yield, waste recycling and good economic value and social value.
The invention relates to a method for preparing graphene by using waste graphite electrodes, which comprises the following steps:
the method comprises the following steps: pretreatment, purification and liquid phase stripping strengthening of waste graphite electrode
The method comprises the steps of obtaining a surface layer from a waste graphite electrode, crushing the surface layer into graphite powder with the particle size of 20-60 microns, placing the graphite powder into a liquid-phase purification stripping solution, purifying and stripping reinforced treatment, controlling the pH value of the liquid-phase purification stripping solution to be 0.5-2 in the treatment process, standing and layering after treatment, separating the upper layer from the lower layer, wherein the upper layer is turbid liquid containing graphene, the lower layer is coarse-grained graphite and indissolvable impurity particles, and separating the upper layer from the lower layer to obtain turbid liquid containing graphene for later use, wherein the liquid-phase purification stripping solution contains aluminum ion salts, and the mass ratio of the aluminum ion salts to the graphite powder is 1: 10-50, taking and adding, wherein the waste graphite electrode is a waste graphite electrode or a waste sodium-ion battery graphite electrode generated in the process of preparing metal through melting electrolysis;
step two: centrifugal classification
Carrying out centrifugal classification on turbid liquid containing graphene to respectively obtain micron-sized particles, submicron-sized particles and suspension containing nano-sized particles, wherein the suspension containing the nano-sized particles is the suspension containing the graphene;
step three: post-treatment
And D, carrying out solid-liquid separation, washing and drying on the suspension containing the graphene obtained in the step two to obtain the graphene.
In the invention, the lower layer separated in the step one can be used as raw materials for recovering coarse-grained graphite and sodium, aluminum and fluorine; the micron-sized particles obtained in the step two are also used as raw materials for recovering coarse-grained graphite and sodium, aluminum and fluorine; and continuously treating the submicron particles obtained in the step two to prepare the graphene.
In the invention, in the first step, the liquid-phase purification delamination liquid containing aluminum ion salt at a specific pH value is used for simultaneously realizing purification and liquid-phase delamination strengthening on graphite powder, and in the whole treatment process, the release of HF in impurities is avoided, so that environment-friendly treatment is realized.
The invention relates to a method for preparing graphene by using a waste graphite electrode. The waste graphite electrode is subjected to heating, metal ion intercalation and electrochemical intercalation in the melting electrolysis process, the electrodes are damaged by the heating, the metal ion intercalation and the electrochemical intercalation, the waste graphite electrode is fully intercalated, and the lamellar structure of the graphite is fully opened. The number of times the waste battery is recycled in the melting electrolysis process is not limited in the invention.
Preferably, in the method for preparing graphene by using the waste graphite electrode, the metal ion radius of the ionic bond metal salt is 50 pm-150 pm. Further preferably, the metal ion of the ionic bonding metal salt is at least one of lithium, aluminum, iron, sodium, potassium, and magnesium.
Preferably, the method for preparing graphene by using the waste graphite electrode comprises the step of preparing graphene by using at least one of fluoride ions and chloride ions which are anions of the ionic bond metal salt.
Preferably, the method for preparing graphene by using the waste graphite electrode comprises one of an aluminum electrolysis production process, a magnesium electrolysis production process, a lithium electrolysis production process, a neodymium electrolysis production process and a lithium-containing alloy production process.
The invention relates to a method for preparing graphene by using a waste graphite electrode, wherein in the step one, the step of obtaining a surface layer from the waste graphite electrode refers to stripping a part with the thickness of 0.5-10 cm from the surface and the inside of a graphite cathode from a waste graphite cathode to the inside of a molten salt electrolytic cell.
The invention discloses a method for preparing graphene by using a waste graphite electrode.
Preferably, in the step one, the pH value of the liquid-phase purification stripping liquid in the treatment process is controlled to be 1-1.5.
The invention relates to a method for preparing graphene by using a waste graphite electrode, which comprises the following steps that in the first step, the mass ratio of graphite powder to liquid-phase purification stripping liquid is 1:10 to 100.
The invention relates to a method for preparing graphene by using a waste graphite electrode, which comprises the step one, wherein the temperature of purification and stripping strengthening treatment is 50-90 ℃, and the time is 0.5-1.0 h.
The invention discloses a method for preparing graphene by using waste graphite electrodes, which comprises the following specific steps of: the specific process of centrifugal classification is as follows: firstly, carrying out low-speed centrifugation, wherein the speed of the low-speed centrifugation is 800-2000 rpm, and the solid obtained by the low-speed centrifugation is micron-sized particles; and carrying out medium-speed centrifugation again on the centrifugal suspension obtained by the low-speed centrifugation, wherein the medium-speed centrifugation speed is 4500-7500 rpm, the centrifugal solid obtained by the medium-speed centrifugation is submicron-grade particles, the centrifugal suspension obtained by the medium-speed centrifugation is a suspension containing the nanoscale particles, the low-speed centrifugation time is 5-30 min, and the medium-speed centrifugation time is 5-30 min.
Preferably, in the second step, the step of continuously processing the submicron particles to prepare the graphene comprises the following steps:
step A electrochemical delamination enhancement
Pressing submicron graphite powder into an electrode slice serving as a cathode, taking a platinum slice as a counter electrode, controlling the voltage of the cathode and the anode to be-5V-30V, and performing electrochemical stripping strengthening treatment to obtain a graphite suspension;
step B mechanical stripping
B, placing the graphite turbid liquid obtained in the step B into a homogenizer, carrying out crushing treatment on the graphite turbid liquid, transferring the graphite turbid liquid into ultrasonic equipment, and carrying out ultrasonic stripping treatment on the graphite turbid liquid to obtain a graphene-containing suspension liquid, wherein the shearing rate of the homogenizer is 50000 s-1～200 000s-1And controlling the frequency of the ultrasonic wave to be 50 kHz-180 kHz, and processing the obtained graphene-containing suspension liquid in the third step to obtain the graphene.
Preferably, in the step a, the electrochemical delamination strengthening electrolyte is composed of a solute and a solvent, the solute is selected from one of n-butyl lithium, tert-butyl lithium, sec-butyl lithium, tetrabutyl ammonium, lithium hexafluorophosphate, sodium perchlorate and sodium hexafluorophosphate, and the solvent is selected from one of propylene carbonate and diethyl carbonate.
Preferably, in the step a, the concentration of the electrolyte solution for the electrochemical delamination strengthening treatment is 0.1mol/L to 3.0 mol/L.
Preferably, in the step A, the voltage of the cathode and the anode is controlled to be-10V to-20V.
Preferably, in the step a, the time of the electrochemical stripping strengthening treatment is 0.5h to 5 h.
Preferably, in the step B, the shear rate of the homogenizer is 120000s-1～180000s-1。
Preferably, in the step B, the treatment temperature in the homogenizer is 5-35 ℃, and the treatment time is 0.5-2 h.
Preferably, in the step B, the frequency of the ultrasonic wave is controlled to be 90 kHz-160 kHz.
Preferably, in the step B, the treatment temperature in the ultrasonic equipment is 20-90 ℃, and the treatment time is 0.5-2 h.
In the invention, the full utilization of raw materials is realized by processing submicron particles.
The method for preparing graphene by using the waste graphite electrode disclosed by the invention is used for preparing the few-layer graphene, and the specific surface area of the prepared few-layer graphene is 500m2/g～2000m2/g。
The principle and advantages of the invention are as follows:
the method takes the waste graphite electrode in the molten salt electrolysis process as a raw material, peels 0.5-10 cm of surface graphite from the waste graphite electrode, and ingeniously utilizes the characteristics that the graphite is fully intercalated and the lamellar structure of the graphite is fully opened due to heating, metal ion intercalation and electrochemical intercalation in the molten salt electrolysis process, so as to obtain the graphene.
In the invention, although the high-temperature intercalation graphite material mainly contains graphite, residual molten salt, molten salt reaction products, petroleum coke and the like, in the aluminum electrolysis process, the high-temperature intercalation graphite electrode material contains residual molten salt sodium aluminate, molten salt reaction products cryolite, aluminum and graphitized petroleum coke, so that the high-temperature intercalation graphite electrode material needs to be purified.
In addition, because the raw material is high-temperature intercalated graphite, the raw material can be subjected to liquid phase exfoliation for strengthening the exfoliation treatment, and the principle of the liquid phase exfoliation is that ions inserted between graphite layers in the high-temperature intercalated graphite are promoted to be released through the liquid phase intercalation treatment, so that the exfoliation of the graphite is strengthened and realized.
According to the invention, purification and liquid phase stripping strengthening are skillfully combined, and the specific liquid phase purification stripping liquid is prepared, so that the purification and the liquid phase stripping strengthening are simultaneously realized, and in addition, in the treatment process, F ions are converted into solids, so that the release of HF is avoided, and the whole treatment process is environment-friendly.
And after purification treatment, carrying out solid-liquid separation, continuously recovering sodium, aluminum, fluorine and coarse-grained graphite from an easily-settled solid phase, and carrying out fine-stage centrifugal separation on a liquid-phase graphite turbid solution. In the centrifugation stage, firstly, low-speed centrifugation is carried out, and the micron-sized particles are separated and used as recovery raw materials of sodium, aluminum, fluorine and coarse-grained graphite; and centrifuging at medium speed to obtain submicron particle graphite, and centrifuging at high speed to obtain suspension containing nano particles, namely directly separating to obtain graphene.
The submicron particles obtained by medium-speed centrifugation belong to particle graphite with the number of layers not reaching the graphene level, so that in subsequent treatment, electrochemical stripping treatment is carried out on the submicron particles, full intercalation is also realized through secondary electrochemical intercalation, and then liquid phase stripping and dispersion of the particle graphite are realized in a subsequent homogenizer and an ultrasonic part.
The method skillfully utilizes the high-temperature intercalated graphite in the waste graphite electrode to perform distinguishing treatment on different states, combines the characteristics, matches appropriate treatment methods and process parameter conditions, and realizes the maximization of yield through the synergistic interaction of all schemes, and the obtained graphene is thin, large in specific surface area and less in stuffing shortage.
The method adopts the waste graphite electrode in the molten salt electrolysis process as the raw material to prepare the graphene, changes waste into valuable, has mild, simple and easily-controlled preparation process, small harm to the environment and people, high yield and good economic and social values, and is suitable for industrial production.
Drawings
FIG. 1 is a flow chart of the test of the present invention.
Detailed Description
The following examples are intended to further illustrate the invention, but not to limit it.
Example 1
First, at room temperature, the solution will be diluted with LiF-Na3AlF6Mechanically stripping intercalated graphite blocks with the thickness of 0.5cm from the surface of a waste cathode graphite electrode generated by molten salt electrolysis of aluminum by taking KF as a raw material, and crushing the intercalated graphite blocks into graphite powder with the thickness of 20 mu m by adopting ball milling equipment; placing graphite powder in a liquid-phase purified stripping liquid containing aluminum chloride, controlling the pH value to be 1.0 by adopting hydrochloric acid, controlling the mass ratio of the graphite powder to the liquid-phase purified stripping liquid to be 1:100, controlling the weight ratio of the aluminum chloride to the graphite powder to be 1:2, stirring and treating at the temperature of 50 ℃ for 0.5h, standing, layering, and separating to obtain a turbid liquid containing graphene on the upper layer for later use, and impurities such as coarse-grained graphite particles on the lower layer as raw materials for recovering coarse-grained graphite, sodium, aluminum and fluorine;
carrying out centrifugal classification on turbid liquid containing graphene, firstly carrying out low-speed centrifugation at the speed of 800rpm for 30min, wherein centrifugal solid obtained by the low-speed centrifugation is micron-sized particles; centrifuging at low speed to obtain centrifugal suspension, centrifuging at intermediate speed of 4500rpm for 30min to obtain centrifugal solid as submicron particles; centrifuging at medium speed to obtain a centrifugal suspension, namely a graphene-containing suspension;
centrifuging the obtained graphene-containing suspension for 30min at the rotation speed of 15000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain graphene, wherein the specific surface area of the prepared graphene material is 1028m2/g。
Preparing the obtained submicron graphite powder into an electrode slice serving as a cathode, taking a platinum slice as a counter electrode, controlling the voltage of the cathode and the anode to be-10V in an electrolyte consisting of sodium hexafluorophosphate and diethyl carbonate, and carrying out electrochemical stripping strengthening treatment for 5 hours to obtain a graphite suspension; the concentration of the electrolyte is 0.1 mol/L.
Placing the obtained graphite suspension in a homogenizer, and controlling the shear rate to be 180000s-1Treating for 0.5h at 5 ℃, then treating by serially connected ultrasonic equipment, controlling the ultrasonic frequency to be 160kHz, the treatment temperature to be 20 ℃, and the treatment time to be 0.5h to obtain the suspension containing graphene. And (3) firstly centrifuging the suspension containing the graphene for 15min under the condition that the rotating speed is 5000rpm, centrifuging the obtained centrifugal suspension for 30min under the condition that the rotating speed is 15000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain the graphene. The specific surface area of the obtained graphene material is 1667m2/g。
In the present invention, the specific surface area of the obtained graphene material fluctuates due to the processing thickness of the surface layer graphite, wherein the specific surface area of the obtained graphene material is the largest when the thickness of the graphite electrode is 0.5 or less, and the specific surface area of the obtained graphene material decreases as the thickness of the taking layer increases, but the utilization rate of the waste graphite electrode increases, so the specific surface area comparison in the present invention needs to be performed for the same thickness.
Example 2
Firstly, mechanically stripping a 10 cm-thick intercalated graphite block from the upper surface of a waste cathode graphite electrode generated by molten salt electrolysis of lithium by taking LiCl-KCl as a raw material at room temperature, and crushing the intercalated graphite block into 60 mu m graphite powder by adopting ball milling equipment; placing graphite powder into a liquid-phase purification stripping liquid containing aluminum nitrate, controlling the pH value to be 1.5 by using nitric acid, wherein the mass ratio of the graphite powder to the liquid-phase purification stripping liquid is 1:10, stirring and treating aluminum nitrate and graphite powder at a weight ratio of 1:3.5 at the temperature of 90 ℃ for 1h, standing for layering, and separating to obtain a turbid liquid containing graphene on the upper layer for later use, and impurities containing coarse-grained graphite particles and the like on the lower layer as raw materials for recovering coarse-grained graphite and sodium, aluminum and fluorine;
carrying out centrifugal classification on turbid liquid containing graphene, firstly carrying out low-speed centrifugation at 2000rpm for 5min, wherein centrifugal solid obtained by the low-speed centrifugation is micron-sized particles; centrifuging at low speed to obtain centrifugal suspension, and centrifuging at intermediate speed of 7500rpm for 5min to obtain submicron-sized solid; centrifuging at medium speed to obtain a centrifugal suspension, namely a graphene-containing suspension;
and centrifuging the obtained suspension containing the graphene for 60min under the condition that the rotating speed is 13000rpm to obtain a centrifugal solid, and washing for 2 times and drying to obtain the graphene. The obtained graphene material has a specific surface area of 629m2/g。
Preparing the obtained submicron graphite powder into an electrode slice serving as a cathode, taking a platinum slice as a counter electrode, controlling the voltage of a cathode and an anode to be-20V in an electrolyte composed of n-butyllithium and propylene carbonate, and performing electrochemical stripping strengthening treatment for 0.5h to obtain a graphite suspension; the concentration of the electrolyte is 3 mol/L.
Placing the obtained graphite suspension in a homogenizer, and controlling the shear rate to be 12000s-1Processing at 35 ℃ for 2h, processing by serially connected ultrasonic equipment, controlling the ultrasonic frequency at 90kHz, the processing temperature at 90 ℃ and the processing time at 2h to obtain a graphene-containing suspension, centrifuging the graphene-containing suspension for 30min under the condition that the rotation speed is 5000rpm, centrifuging the obtained centrifugal suspension for 60min under the condition that the rotation speed is 15000rpm, washing the obtained centrifugal solid for 2 times, and drying to obtain the graphene. The specific surface area of the obtained graphene material is 754m2/g。
Example 3
Firstly, at room temperature, the solution is mixed with NdF3-LiF-Nd2O3Mechanically stripping an intercalated graphite block with the thickness of 1cm from the surface of a waste cathode graphite electrode generated by electrolyzing lithium by using a molten salt as a raw material, and crushing the intercalated graphite block into graphite powder with the thickness of 30 mu m by using ball milling equipment; placing graphite powder in a liquid-phase purified stripping liquid containing aluminum chloride, controlling the pH value to be 1.0 by hydrochloric acid, controlling the mass ratio of the graphite powder to the liquid-phase purified stripping liquid to be 1:80 and the weight ratio of the aluminum chloride to the graphite powder to be 1:3, stirring at the temperature of 60 ℃ for 40min, standing for layering, and separating to obtain a turbid liquid containing graphene on the upper layer and impurities containing coarse-grained graphite particles and the like on the lower layer as raw materials for recovering coarse-grained graphite and sodium, aluminum and fluorine;
carrying out centrifugal classification on turbid liquid containing graphene, firstly carrying out low-speed centrifugation at the speed of 1000rpm for 20min, wherein centrifugal solid obtained by the low-speed centrifugation is micron-sized particles; centrifuging at medium speed of 5500rpm for 20min to obtain centrifugal suspension, wherein the centrifugal solid obtained by the medium speed centrifugation is submicron particles; centrifuging at medium speed to obtain a centrifugal suspension, namely a graphene-containing suspension;
and centrifuging the obtained graphene-containing suspension for 40min at the rotation speed of 14000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain the graphene. The obtained graphene material has a specific surface area of 926m2/g。
Preparing the obtained submicron graphite powder into an electrode slice serving as a cathode, taking a platinum slice as a counter electrode, controlling the voltage of a cathode and an anode to be-15V in an electrolyte consisting of lithium hexafluorophosphate and diethyl carbonate, and performing electrochemical stripping strengthening treatment for 3h to obtain a graphite suspension; the concentration of the electrolyte is 1 mol/L.
Placing the obtained graphite suspension in a homogenizer, and controlling the shear rate to 150000 s-1Treating at 10 ℃ for 45min, then treating by serially connected ultrasonic equipment, controlling the ultrasonic frequency at 150kHz, the treatment temperature at 30 ℃ and the treatment time at 45min to obtain the graphene-containing suspension. And (3) firstly centrifuging the suspension containing the graphene for 20min under the condition that the rotating speed is 5000rpm, centrifuging the obtained centrifugal suspension for 40min under the condition that the rotating speed is 15000rpm, washing the obtained centrifugal solid for 2 times, and drying to obtain the graphene. The specific surface area of the obtained graphene material is 1148m2/g。
Example 4
First, at room temperature, LiCl-LiF-BaF will be used2Mechanically stripping an intercalated graphite block with the thickness of 8cm from the upper surface of a waste cathode graphite electrode generated by electrolyzing Cu-Li alloy by using a raw material molten salt, and crushing the intercalated graphite block into graphite powder with the thickness of 40 mu m by using ball milling equipment; placing graphite powder into a liquid-phase purification stripping liquid containing aluminum nitrate, controlling the pH value to be 1.5 by using nitric acid, wherein the mass ratio of the graphite powder to the liquid-phase purification stripping liquid is 1: 20, the weight ratio of the aluminum nitrate to the graphite powder is 1:2.5, and the temperature is controlledStirring at 70 deg.C for 50min, standing for layering, separating to obtain upper layer turbid solution containing graphene, and lower layer impurity containing coarse-grained graphite particles as coarse-grained graphite and raw materials for recovering sodium, aluminum and fluorine;
carrying out centrifugal classification on turbid liquid containing graphene, firstly carrying out low-speed centrifugation at 1500rpm for 10min, wherein centrifugal solid obtained by the low-speed centrifugation is micron-sized particles; centrifuging at a medium speed of 6500rpm for 10min to obtain a centrifugal suspension, wherein the centrifugal solid obtained by the medium speed centrifugation is submicron particles; centrifuging at medium speed to obtain a centrifugal suspension, namely a graphene-containing suspension;
and centrifuging the obtained graphene-containing suspension for 40min at the rotation speed of 15000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain the graphene. The specific surface area of the obtained graphene material is 656m2/g。
Preparing the obtained submicron graphite powder into an electrode slice serving as a cathode, taking a platinum slice as a counter electrode, controlling the voltage of the cathode and the anode to be-17V in an electrolyte consisting of sodium perchlorate and propylene carbonate, and performing electrochemical stripping strengthening treatment for 1h to obtain a graphite suspension; the concentration of the electrolyte is 2 mol/L.
Placing the obtained graphite suspension in a homogenizer, and controlling the shear rate to 13000s-1Processing at 30 ℃ for 100min, processing by serially connected ultrasonic equipment, controlling the operating frequency to be 100kHz, the processing temperature to be 70 ℃ and the time to be 100min to obtain a graphene-containing suspension, centrifuging the graphene-containing suspension for 30min under the condition that the rotating speed is 5000rpm, centrifuging the obtained centrifugal suspension for 50min under the condition that the rotating speed is 15000rpm, washing the obtained centrifugal solid for 2 times, and drying to obtain the graphene. The specific surface area of the graphene material prepared from the obtained graphene material is 881m2/g。
Example 5
First, at room temperature, MgCl will be used2Mechanically stripping intercalated graphite blocks with the thickness of 2cm from the surface of a waste cathode graphite electrode generated by fused salt magnesium electrolysis by using NaCl-KCl as a raw material, and crushing the intercalated graphite blocks into graphite powder with the thickness of 40 mu m by adopting ball milling equipment; mixing graphite powderPlacing the mixture into a liquid-phase purified stripping liquid containing aluminum chloride, controlling the pH value to be 1.2 by adopting hydrochloric acid, controlling the mass ratio of graphite powder to the liquid-phase purified stripping liquid to be 1:60 and the weight ratio of aluminum chloride to graphite powder to be 1:4, stirring and treating at the temperature of 55 ℃ for 45min, standing for layering, separating to obtain a turbid liquid containing graphene on the upper layer for later use, and impurities containing coarse-grained graphite particles and the like on the lower layer as raw materials for recovering the coarse-grained graphite and sodium, aluminum and fluorine;
carrying out centrifugal classification on turbid liquid containing graphene, firstly carrying out low-speed centrifugation at the speed of 1200rpm for 15min, wherein centrifugal solid obtained by the low-speed centrifugation is micron-sized particles; centrifuging at medium speed of 5000rpm for 15min to obtain centrifugal suspension, and centrifuging at medium speed to obtain submicron particles; centrifuging at medium speed to obtain a centrifugal suspension, namely a graphene-containing suspension;
and centrifuging the obtained graphene-containing suspension for 30min at the rotation speed of 15000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain the graphene. The specific surface area of the obtained graphene material is 718m2/g。
Preparing the obtained submicron graphite powder into an electrode slice serving as a cathode, taking a platinum slice as a counter electrode, controlling the voltage of the cathode and the anode to be-13V in an electrolyte consisting of tetrabutylammonium and diethyl carbonate, and performing electrochemical stripping strengthening treatment for 2.5h to obtain a graphite suspension; the concentration of the electrolyte is 0.8 mol/L.
Placing the obtained graphite suspension in a homogenizer, and controlling the shear rate to 160000 s-1Processing at 15 ℃ for 1h, then processing by serially connected ultrasonic equipment, controlling the ultrasonic frequency to be 120kHz, the processing temperature to be 40 ℃, and the processing time to be 1h to obtain the suspension containing graphene. And (3) firstly centrifuging the suspension containing the graphene for 25min under the condition that the rotating speed is 5000rpm, centrifuging the obtained centrifugal suspension for 45min under the condition that the rotating speed is 15000rpm, washing for 2 times, and drying the centrifugal solid to obtain the graphene. The specific surface area of the graphene material prepared from the obtained graphene material is 882m2/g。
Example 6
First, at room temperature, the solution will be diluted with LiF-Na3AlF6Mechanically stripping an intercalated graphite block with the thickness of 5cm from the upper surface of a waste cathode graphite electrode generated by molten salt electrolysis of aluminum by taking KF as a raw material, and crushing the intercalated graphite block into graphite powder with the thickness of 50 mu m by adopting ball milling equipment; placing graphite powder into a liquid-phase purification stripping liquid containing aluminum nitrate, controlling the pH value to be 1.4 by using nitric acid, wherein the mass ratio of the graphite powder to the liquid-phase purification stripping liquid is 1: 40, stirring and treating the aluminum nitrate and the graphite powder at the weight ratio of 1:2 at the temperature of 60 ℃ for 50min, standing for layering, and separating to obtain a turbid liquid containing graphene on the upper layer for later use, and impurities containing coarse-grained graphite particles and the like on the lower layer as raw materials for recovering the coarse-grained graphite and sodium, aluminum and fluorine;
carrying out centrifugal classification on turbid liquid containing graphene, firstly carrying out low-speed centrifugation at 1300rpm for 20min, wherein centrifugal solid obtained by the low-speed centrifugation is micron-sized particles; centrifuging at 7000rpm for 20min to obtain submicron particle; centrifuging at medium speed to obtain a centrifugal suspension, namely a graphene-containing suspension;
and centrifuging the obtained graphene-containing suspension for 40min under the condition that the rotating speed is 15000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain the graphene. The specific surface area of the graphene material prepared from the obtained graphene material is 575m2/g。
Preparing the obtained submicron graphite powder into an electrode slice serving as a cathode, taking a platinum slice as a counter electrode, controlling the voltage of the cathode and the anode to be-14V in an electrolyte consisting of sec-butyl lithium and propylene carbonate, and performing electrochemical stripping strengthening treatment for 3h to obtain a graphite suspension; the concentration of the electrolyte is 2.5 mol/L.
Placing the obtained graphite suspension in a homogenizer, and controlling the shear rate to 14000s-1Treating at 20 ℃ for 1.5h, treating by serially connected ultrasonic equipment, controlling the frequency at 110kHz, the treatment temperature at 40 ℃ and the time at 1.5h to obtain a graphene-containing suspension, centrifuging the graphene-containing suspension at the rotation speed of 5000rpm for 30min, centrifuging the obtained centrifugal suspension at the rotation speed of 15000rpm for 60min to obtain a centrifugal solid, washing for 2 times, and drying to obtain graphene. The specific surface area of the graphene material prepared from the obtained graphene material is 729m2/g。
Comparative example 1
The other conditions were the same as in example 1 except that: aluminum chloride is not added, and a large amount of HF gas is discharged in the stirring process, so that the test environment is seriously polluted.
Comparative example 2
The other conditions were the same as in example 1 except that: in the liquid phase purification process, the pH value of hydrochloric acid is controlled to be 3.0. The specific surface areas of the finally obtained two parts of graphene materials are 846m respectively2Per g and 1059m2/g。
Comparative example 3
First, at room temperature, the solution will be diluted with LiF-Na3AlF6Mechanically stripping intercalated graphite blocks with the thickness of 0.5cm from the surface of a waste cathode graphite electrode generated by molten salt electrolysis of aluminum by taking KF as a raw material, and crushing the intercalated graphite blocks into graphite powder with the thickness of 20 mu m by adopting ball milling equipment; placing graphite powder in a liquid-phase purified stripping liquid containing aluminum chloride, controlling the pH value to be 1.0 by adopting hydrochloric acid, controlling the mass ratio of the graphite powder to the liquid-phase purified stripping liquid to be 1:100, controlling the weight ratio of the aluminum chloride to the graphite powder to be 1:2, stirring and processing at 50 ℃ for 0.5h, standing for layering, separating to obtain a turbid liquid containing graphene on the upper layer for later use, and using impurities such as coarse-grained graphite particles and the like on the lower layer as raw materials for recovering coarse-grained graphite and sodium, aluminum and fluorine;
carrying out centrifugal classification on turbid liquid containing graphene, firstly carrying out low-speed centrifugation at the speed of 800rpm for 30min, wherein centrifugal solid obtained by the low-speed centrifugation is micron-sized particles; centrifuging at a medium speed of 4500rpm for 30min to obtain a centrifugal suspension, wherein the centrifugal solid obtained by the medium speed centrifugation is submicron particles; centrifuging at medium speed to obtain a centrifugal suspension, namely a graphene-containing suspension;
and centrifuging the obtained graphene-containing suspension for 30min under the condition that the rotating speed is 15000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain the graphene. The specific surface area of the obtained graphene material is 982m2/g。
Placing the obtained submicron graphite powder into a homogenizing wayIn-machine, the shear rate was controlled to 180000s-1And treating for 0.5h at 5 ℃, treating by serially connected ultrasonic equipment, controlling the ultrasonic frequency to be 160kHz, the treatment temperature to be 20 ℃, and the treatment time to be 0.5h to obtain the suspension containing graphene. And (3) firstly centrifuging the suspension containing the graphene for 15min under the condition that the rotating speed is 5000rpm, centrifuging the obtained centrifugal suspension for 30min under the condition that the rotating speed is 15000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain the graphene. The specific surface area of the obtained graphene material is 639m2/g。
Comparative example 4
Firstly, mechanically stripping a 10 cm-thick intercalated graphite block from the upper surface of a waste cathode graphite electrode generated by molten salt electrolysis of lithium by taking LiCl-KCl as a raw material at room temperature, and crushing the intercalated graphite block into 60 mu m graphite powder by adopting ball milling equipment; placing graphite powder into a liquid-phase purification stripping liquid containing aluminum nitrate, controlling the pH value to be 1.5 by using nitric acid, wherein the mass ratio of the graphite powder to the liquid-phase purification stripping liquid is 1:10, stirring and treating aluminum nitrate and graphite powder at a weight ratio of 1:3.5 at the temperature of 90 ℃ for 1h, standing for layering, and separating to obtain a turbid liquid containing graphene on the upper layer for later use, and impurities containing coarse-grained graphite particles and the like on the lower layer as raw materials for recovering coarse-grained graphite and sodium, aluminum and fluorine;
carrying out centrifugal classification on turbid liquid containing graphene, firstly carrying out low-speed centrifugation at 2000rpm for 5min, wherein centrifugal solid obtained by the low-speed centrifugation is micron-sized particles; centrifuging at a medium speed of 7500rpm for 5min to obtain a centrifugal suspension liquid, wherein the centrifugal solid obtained by the medium speed centrifugation is submicron particles; centrifuging at medium speed to obtain a centrifugal suspension, namely a graphene-containing suspension;
and centrifuging the obtained graphene-containing suspension for 60min under the condition that the rotation speed is 13000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain the graphene. The specific surface area of the obtained graphene material is 705m2/g。
Preparing the obtained submicron graphite powder into an electrode slice serving as a cathode, taking a platinum slice as a counter electrode, controlling the voltage of a cathode and an anode to be-20V in an electrolyte composed of n-butyllithium and propylene carbonate, and performing electrochemical stripping strengthening treatment for 0.5h to obtain a graphite suspension; the concentration of the electrolyte is 3 mol/L.
And (3) treating the obtained graphite suspension in ultrasonic equipment with the frequency of 90kHz, wherein the treatment temperature is 90 ℃ and the treatment time is 2h, obtaining graphene-containing suspension, firstly centrifuging the graphene-containing suspension for 30min under the condition that the rotation speed is 5000rpm, then centrifuging the obtained centrifugal suspension for 60min under the condition that the rotation speed is 15000rpm, washing for 2 times, and drying the centrifuged solid to obtain the graphene. The obtained graphene material has a specific surface area of 469m2/g。
Comparative example 5
Firstly, at room temperature, the solution is mixed with NdF3-LiF-Nd2O3Mechanically stripping an intercalated graphite block with the thickness of 1cm from the surface of a waste cathode graphite electrode generated by electrolyzing lithium by using a molten salt as a raw material, and crushing the intercalated graphite block into graphite powder with the thickness of 30 mu m by using ball milling equipment; placing graphite powder in a liquid-phase purified stripping liquid containing aluminum chloride, controlling the pH value to be 1.0 by hydrochloric acid, controlling the mass ratio of the graphite powder to the liquid-phase purified stripping liquid to be 1:80 and the weight ratio of the aluminum chloride to the graphite powder to be 1:3, stirring at the temperature of 60 ℃ for 40min, standing for layering, and performing solid-liquid separation to obtain a turbid liquid containing graphene on the upper layer and impurities such as coarse-grained graphite particles on the lower layer as raw materials for recovering coarse-grained graphite and sodium, aluminum and fluorine;
carrying out centrifugal classification on turbid liquid containing graphene, and firstly centrifuging at a low speed of 1000rpm for 20min to obtain centrifugal solid which is micron-sized particles; centrifuging the suspension at 5500rpm for 20min to obtain submicron particles; centrifuging the suspension to obtain the suspension containing graphene;
and centrifuging the obtained graphene-containing suspension for 40min at the rotation speed of 14000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain the graphene. The specific surface area of the obtained graphene material is 939m2/g。
Preparing the obtained submicron graphite powder into an electrode slice serving as a cathode, taking a platinum slice as a counter electrode, controlling the voltage of a cathode and an anode to be-15V in an electrolyte consisting of lithium hexafluorophosphate and diethyl carbonate, and performing electrochemical stripping strengthening treatment for 3h to obtain a graphite suspension; the concentration of the electrolyte is 1 mol/L.
Placing the obtained graphite suspension in a homogenizer, and controlling the shear rate to 150000 s-1And treating at 10 ℃ for 45min to obtain the graphene-containing suspension. And (3) firstly centrifuging the suspension containing the graphene for 20min under the condition that the rotating speed is 5000rpm, centrifuging the obtained centrifugal suspension for 40min under the condition that the rotating speed is 15000rpm to obtain a centrifugal solid, washing for 2 times, and drying to obtain the graphene. The obtained graphene material has a specific surface area of 728m2/g。
Comparative example 6
Firstly, crushing pure graphite into graphite powder with the particle size of 20 microns by adopting ball milling equipment at room temperature; placing graphite powder in liquid-phase purified stripping liquid containing aluminum chloride, controlling the pH value to be 1.0 by adopting hydrochloric acid, controlling the mass ratio of the graphite powder to the liquid-phase purified stripping liquid to be 1:100, controlling the weight ratio of the aluminum chloride to the graphite powder to be 1:2, stirring at the temperature of 50 ℃ for 0.5h, standing for layering, and finding out that the upper-layer liquid phase is clear;
centrifuging and grading the separated supernatant, and centrifuging at a low speed of 800rpm for 30min to find that no centrifugal solid is obtained; centrifuging the upper layer liquid at 4500rpm for 30min to obtain solid; the supernatant liquid from the medium speed centrifugation was centrifuged at 15000rpm for 30min, and no centrifuged solid was obtained.
Those of ordinary skill in the art will understand that: the invention is not to be considered as limited to the specific embodiments thereof, but is to be understood as being modified in all respects, all changes and equivalents that come within the spirit and scope of the invention.
Claims (10)
1. A method for preparing graphene by using a waste graphite electrode is characterized by comprising the following steps:
the method comprises the following steps: pretreatment, purification and liquid phase stripping strengthening of waste graphite electrode
The method comprises the steps of obtaining a surface layer from a waste graphite electrode, crushing the surface layer into graphite powder with the particle size of 20-60 microns, placing the graphite powder into a liquid-phase purification stripping solution, purifying and stripping reinforced treatment, controlling the pH value of the liquid-phase purification stripping solution to be 0.5-2 in the treatment process, standing and layering after treatment, separating the upper layer from the lower layer to obtain a turbid solution containing graphene, wherein the upper layer is a turbid solution containing graphene, the lower layer is coarse-grained graphite and insoluble impurity particles, and the upper layer and the lower layer are separated to obtain the turbid solution containing graphene for later use, the liquid-phase purification stripping solution contains an aluminum ion salt, and the mass ratio of the aluminum ion salt to the graphite powder is 1: 10-50, taking and adding, wherein the waste graphite electrode is a waste graphite electrode generated in the process of preparing metal by adding ionic bond metal salt through melting electrolysis;
step two: centrifugal classification
Carrying out centrifugal classification on turbid liquid containing graphene to respectively obtain micron-sized particles, submicron-sized particles and suspension containing nano-sized particles, wherein the suspension containing the nano-sized particles is the suspension containing the graphene;
step three: post-treatment
And D, carrying out solid-liquid separation, washing and drying on the suspension containing the graphene obtained in the step two to obtain the graphene.
2. The method for preparing graphene by using the waste graphite electrode as claimed in claim 1, wherein the method comprises the following steps: in the first step, the metal ion radius of the ionic bond metal salt is 50 pm-150 pm; the anion of the ionic bond metal salt is at least one of fluoride ion and chloride ion.
3. The method for preparing graphene by using the waste graphite electrode as claimed in claim 1, wherein the method comprises the following steps: in the first step, the aluminum ion salt is at least one of aluminum chloride and aluminum nitrate, and the pH value of the liquid-phase purification stripping solution is regulated and controlled by hydrochloric acid or nitric acid.
4. The method for preparing graphene by using the waste graphite electrode as claimed in claim 1, wherein the method comprises the following steps: in the first step, the mass ratio of the graphite powder to the liquid-phase purification stripping liquid is 1:10 to 100 parts; in the first step, the temperature of the purification and stripping strengthening treatment is 50-90 ℃ and the time is 0.5-1.0 h.
5. The method for preparing graphene by using the waste graphite electrode as claimed in claim 1, wherein the method comprises the following steps: in the second step, the specific process of centrifugal classification is as follows: firstly, carrying out low-speed centrifugation, wherein the speed of the low-speed centrifugation is 800-2000 rpm, and the solid obtained by the low-speed centrifugation is micron-sized particles; and carrying out medium-speed centrifugation again on the centrifugal suspension obtained by the low-speed centrifugation, wherein the medium-speed centrifugation speed is 4500-7500 rpm, the centrifugal solid obtained by the medium-speed centrifugation is submicron-grade particles, the centrifugal suspension obtained by the medium-speed centrifugation is a suspension containing the nanoscale particles, the low-speed centrifugation time is 5-30 min, and the medium-speed centrifugation time is 5-30 min.
6. The method for preparing graphene by using the waste graphite electrode according to claim 1, wherein in the second step, the submicron particles are further processed to prepare graphene in the following steps:
step A electrochemical delamination enhancement
Pressing submicron graphite powder into an electrode slice serving as a cathode, taking a platinum slice as a counter electrode, controlling the voltage of the cathode and the anode to be-5V-30V, and performing electrochemical stripping strengthening treatment to obtain a graphite suspension;
step B mechanical stripping
B, placing the graphite turbid liquid obtained in the step B into a homogenizer, carrying out crushing treatment on the graphite turbid liquid, transferring the graphite turbid liquid into ultrasonic equipment, and carrying out ultrasonic stripping treatment on the graphite turbid liquid to obtain a graphene-containing suspension liquid, wherein the shearing rate of the homogenizer is 50000 s-1～200000s-1And controlling the frequency of the ultrasonic wave to be 50 kHz-180 kHz, and processing the obtained graphene-containing suspension liquid in the third step to obtain the graphene.
7. The method for preparing graphene using the waste graphite electrode according to claim 6, wherein the electrochemical delamination strengthening treatment electrolyte in the step A is composed of a solute and a solvent, the solute is selected from one of n-butyllithium, tert-butyllithium, sec-butyllithium, tetrabutylammonium, lithium hexafluorophosphate, sodium perchlorate and sodium hexafluorophosphate, the solvent is selected from one of propylene carbonate and diethyl carbonate, and the concentration of the electrochemical delamination strengthening treatment electrolyte is 0.1mol/L to 3.0 mol/L.
8. The method for preparing graphene by using the waste graphite electrode as claimed in claim 6, wherein in the step A, the voltage of the cathode and the anode is controlled to be-10V to-20V, and the time of the electrochemical stripping strengthening treatment is 0.5h to 5 h.
9. The method for preparing graphene by using the waste graphite electrode as claimed in claim 6, wherein the method comprises the following steps: in the step B, the shear rate of the homogenizer is 120000s-1～180 000s-1The treatment temperature in the homogenizer is 5-35 ℃, and the treatment time is 0.5-2 h.
10. The method for preparing graphene by using the waste graphite electrode as claimed in claim 6, wherein the method comprises the following steps: in the step B, the ultrasonic frequency is controlled to be 90 kHz-160 kHz, the processing temperature in the ultrasonic equipment is 20 ℃ to 90 ℃, and the processing time is 0.5h to 2 h.
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